CN104549401A - Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application - Google Patents

Abstract

The invention discloses a non-metallic catalyst for acetylene hydrochlorination and its preparation method and application. The preparation method is as follows: dissolving a non-metallic compound containing at least one of N, O, S and P in a solvent, and putting it in a water bath for 30 ℃-100℃, stir to dissolve the impregnating liquid; immerse the catalyst carrier in the impregnating liquid, seal and stir for impregnation, filter and filter out the liquid; dry, put in a tube furnace or muffle furnace, heat up in a nitrogen atmosphere, keep , cooled to room temperature to obtain a metal-free catalyst for acetylene hydrochlorination. Using the catalyst of the present invention reduces the environmental pollution caused by metal catalysts; under the conditions of reaction temperature of 170°C, acetylene space velocity of 180h ^-1 , raw material gas ratio V _C2H2 /V _HC1 =1:1.15, the acetylene The initial conversion rate can be increased by 10%-200% compared with the activated carbon catalyst that does not support non-metallic components, and the selectivity of forming vinyl chloride is greater than 99.0%.

Description

A kind of non-metallic catalyst for acetylene hydrochlorination and its preparation method and application

technical field

The invention relates to a non-metallic catalyst for acetylene hydrochlorination, a preparation method and application thereof. It belongs to the preparation technology and application scope of catalysts for organic synthesis.

Background technique

With the development of the national economy, the improvement of people's living standards and the improvement of environmental protection awareness, the demand for PVC (polyvinyl chloride) is increasing. PVC is obtained by polymerization of VCM (vinyl chloride monomer). The production methods of VCM mainly include ethylene process, ethane process and acetylene process. Because foreign oilfields are rich in ethylene and the raw materials are cheap, developed countries generally adopt the ethylene method to produce VCM; the raw material cost of VCM prepared by the ethane method is low, but requires relatively high investment. There is still a certain distance from industrialization; the limitation of the preparation of VCM by the acetylene process is mainly due to the supply of raw materials, the high cost of raw materials and the limitation of production capacity. Due to the distribution of resources in our country, the raw material gas ethylene is not abundant, it has always been lacking and the price is high, and with the depletion of petrochemical resources, my country has a large amount of low-cost coal that provides raw materials and price advantages, so our country is suitable for acetylene The French route mainly produces VCM. Therefore, in the western region, such as Xinjiang, Inner Mongolia and other areas rich in coal resources, the new or expanded calcium carbide production of polyvinyl chloride resin projects is developing rapidly. However, the fatal bottleneck problem that restricts the acetylene method to become green chemistry is the catalyst problem. The main active ingredient of the catalyst used in the industry is mercury chloride. Mercury is easily lost by sublimation and is a serious pollution source in the production of polyvinyl chloride by the calcium carbide method. The calcium carbide process consumes about 1.4 kilograms of mercury for every ton of PVC produced. According to statistics, in 2010, the amount of mercury used in my country's acetylene-based PVC industry was about 767 tons, accounting for more than 60% of the country's mercury consumption and the world's mercury consumption. About 20% of the total. The loss of mercury not only causes the catalyst to be deactivated, but also the catalyst cannot be regenerated due to the loss of active components, which also affects the quality of VCM products and causes great harm to the ecological environment. In addition, mercury is a heavy metal, highly toxic, and the concentration of toxicity is 0.01 ~ 0.1mg/l, and it cannot be degraded by microorganisms. It can only migrate and transform between water and organisms in different valence states, and disperse and enrich After entering the human body, it is difficult to metabolize it. It gathers in the liver, kidney and brain, damages the nervous system, and causes the terrible "Minamata disease". It is predicted that by 2014, the consumption of mercury in the production of PVC resin by acetylene method will reach 175,489 tons. Mercury has also attracted much attention because of its potential huge harm. Therefore, what needs to be solved urgently at present is the pollution problem caused by mercury catalysts. Research on non-mercury catalysts that replace mercury chloride catalysts will affect the survival of enterprises producing PVC by acetylene method, environmental problems, economic development, improvement of people's living standards, and construction of a harmonious society. to great effect.

Hutchings et al. used more than 20 metal components for acetylene hydrochlorination, and concluded that the activity of the components is related to the standard electrode potential. The order of initial activity is Pd ²⁺ >Hg ²⁺ >Cu ²⁺ , Cu ⁺ >Ag ⁺ ; M.Conte etc. have studied in detail the bimetallic catalysts of activated carbon supported gold catalyst 1wt% Au/C and Pd, Pt, Ir, Rh, Ru and Au and the mechanism of acetylene hydrochlorination reaction; Wei Fei et al prepared _SiO2 is used as a carrier, bismuth, copper, barium, zinc, cadmium and other chlorides or phosphates are mercury-free catalysts as active components, and their activity in acetylene hydrochlorination has been tested. PO ₄ ^3- significantly improves the catalytic activity, especially the composite phosphate of Bi and Cu. At a reaction temperature of 200°C, its initial reaction activity is 1/3 of that of industrial catalysts, and it has certain reproducibility. Chen Rongti etc. prepared and investigated three-component stannous chloride-bismuth trichloride-cuprous chloride/activated carbon mercury-free catalyst, its initial activity and selectivity are close to high mercury chloride/activated carbon catalyst, and its lifespan is 120 hours, but chlorine Stannous chloride is also a volatile substance, which cannot solve the catalyst deactivation.

Therefore, although people at home and abroad are currently committed to the research of mercury-free catalysts, most of the research content is concentrated on the screening and compounding of metal active components. The catalysts developed also have low activity, poor stability, and are prone to deactivation and The problem of not being easy to regenerate, the lifespan is short, and the economy is not high, which brings great restrictions to its industrial production.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art and provide a non-metallic catalyst for acetylene hydrochlorination.

The second object of the present invention is to provide a method for the preparation of a metal-free catalyst for acetylene hydrochlorination.

The third object of the present invention is to provide a kind of non-metallic catalyst for acetylene hydrochlorination in the application of acetylene hydrochlorination.

Technical scheme of the present invention is summarized as follows:

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 0.1-10g of a non-metallic compound containing at least one of N, O, S and P in 10-50ml of solvent in proportion, and stir to dissolve to obtain an impregnation solution; the solvent is water, methanol, ethanol, formaldehyde , acetic acid, hot ethylene glycol, glycerin, pyridine, acetone, N-methylpyrrolidone, ether, benzene, chloroform;

(2) Proportionally immerse 10g of the catalyst carrier into the impregnation solution, in a water bath at 30-100°C, seal and stir for 2-10h, filter the liquid; dry it, put it into a tube furnace or a muffle furnace, and Under a nitrogen atmosphere, raise the temperature to 500-1000° C. at a rate of 4-6° C./min, keep it for 1-4 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination.

The non-metallic compound containing N is melamine, urea, pyrrole, pyridine, pyrimidine or purine.

The non-metallic compound containing O is nitric acid or hydrogen peroxide.

The non-metallic compound containing S is thiourea or thiol.

The non-metal compound containing P is triphenylphosphine, sodium hypophosphite, pyrophosphoric acid or sodium pyrophosphate.

The catalyst carrier is coconut shell activated carbon, coal-based activated carbon, pitch-based spherical activated carbon, carbon nanotube, silicon carbide, ZTCMS-185 molecular sieve, ZTCMS-200 molecular sieve or ZTCMS-220 molecular sieve.

A non-metallic catalyst for acetylene hydrochlorination prepared by the above method.

The application of a metal-free catalyst for acetylene hydrochlorination in acetylene hydrochlorination.

Advantages of the present invention:

Using a non-metallic catalyst of the present invention to replace the traditional metal catalyst reduces the pollution caused by the metal catalyst to the environment; when the reaction temperature is 170°C, the acetylene space velocity is 180h ^-1 , and the raw material gas ratio V _C2H2 /V _HC1 = Under the condition of 1:1.15, the initial conversion rate of acetylene can be increased by 10%-200% compared with the activated carbon catalyst without non-metallic components, and the selectivity to vinyl chloride is greater than 99.0%.

Detailed ways

The present invention is specifically described below through examples, so that those skilled in the art can better understand the present invention. However, the examples given are not intended to limit the present invention.

Example 1

Test of coconut shell activated carbon (reference) as catalyst for acetylene hydrochlorination

In the equipment, the reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, ratio of raw material gas V _C2H2 /V _HC1 =1:1.15, pretreated activated carbon loading volume is 5ml;

The activated carbon catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 15.0%, and the selectivity of vinyl chloride is greater than 99.0%.

Example 2

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 1 g of melamine in 25 ml of formaldehyde, and stir to dissolve in a water bath at 60°C to obtain an impregnating solution;

(2) Immerse 10g of coconut shell activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 2h, filter the liquid; Raise the heating rate to 500°C, keep it for 4 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above-mentioned catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above-mentioned conditions, and the initial conversion rate of acetylene is 25%, and the selectivity of vinyl chloride is greater than 99%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 66.7%.

Experiments have proved that the impregnation solution prepared by using acetic acid, hot ethylene glycol, glycerin or pyridine instead of formaldehyde in this example as the solvent can also be used for the preparation of non-metallic catalysts for acetylene hydrochlorination.

Example 3

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of triphenylphosphine in 20ml of methanol, and stir to dissolve in a water bath at 100°C to obtain an impregnating solution;

(2) Immerse 10g of carbon nanotubes in the impregnating solution, in a water bath at 100°C, seal and stir for 2 hours, filter and filter off the liquid; dry, put in a muffle furnace, and heat at 6°C/min under a nitrogen atmosphere Raise the heating rate to 1000°C, keep it for 1h, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 20.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 33.3%.

Experiments have proved that the impregnation solution prepared by using chloroform instead of methanol in this example as the solvent can also be used for the preparation of non-metallic catalysts for acetylene hydrochlorination.

Example 4

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Weigh 10g of 30% hydrogen peroxide and dissolve it in 20ml of ether, and stir to dissolve in a water bath at 30°C to obtain an impregnation solution;

(2) Immerse 10g of pitch-based spherical activated carbon into the impregnating solution, in a water bath at 30°C, impregnate with sealing and stirring for 10h, filter the liquid; The heating rate is raised to 800°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 30.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 100.0%.

Example 5

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 5g of thiourea in 30ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnating solution;

(2) Immerse 10g of pitch-based spherical activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 4 hours, filter and filter off the liquid; dry it, put it in a tube furnace, and heat it in a nitrogen atmosphere at 5°C/min The heating rate is raised to 800°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 28.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 86.7%.

Example 6

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 0.1g of urea in 10ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnating solution;

(2) Immerse 10g of silicon carbide into the impregnation solution, in a water bath at 60°C, seal and stir for 4h, filter and filter off the liquid; dry, put in a tube furnace, and heat up at a rate of 5°C/min under a nitrogen atmosphere Raise the rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h-1, reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 16.5%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 10.0%.

Example 7

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of pyrrole + 3g of sodium hypophosphite in 45ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of ZTCMS-200 molecular sieve into the impregnating solution, in a water bath at 60°C, seal and stir for 4h, filter and filter off the liquid; The heating rate of min was raised to 800 ° C, kept for 2 hours, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 33.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 120.0%.

Example 8

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of melamine + 1g of mercaptan in 30ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnating solution;

(2) Immerse 10g of ZTCMS-185 molecular sieve into the impregnating solution, in a water bath at 60°C, seal and stir for 4h, filter and filter off the liquid; The heating rate of min was raised to 800°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above-mentioned catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above-mentioned conditions, and the initial conversion rate of acetylene is 27.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 80.0%.

Example 9

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of concentrated nitric acid + 3g of thiourea in 35ml of water, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of ZTCMS-220 molecular sieve into the impregnating solution, in a water bath at 60°C, seal and stir for 4h, filter and filter off the liquid; The heating rate of min was raised to 800°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 22.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 46.7%.

Example 10

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of concentrated nitric acid + 2g of sodium pyrophosphate in 40ml of water, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of coal-based activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 4h, filter the liquid; Raise the heating rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 38.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 153.3%.

Example 11

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of thiourea + 1g of triphenylphosphine in 35ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of coconut shell activated carbon into the impregnation solution, in a water bath at 60°C, seal and stir for 4 hours, filter and filter off the liquid; dry, put it into a tube furnace, and heat it at a rate of 5°C/min under a nitrogen atmosphere. Raise the heating rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 21.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 40.0%.

Example 12

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of melamine + 3g of 30% hydrogen peroxide + 1g of thiourea in 30ml of absolute ethanol, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of coal-based activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 6h, filter and filter off the liquid; Raise the heating rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 40.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 166.7%.

Example 13

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of pyridine + 3g of concentrated nitric acid + 3g of sodium hypophosphite in 40ml of water, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of coal-based activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 6h, filter and filter off the liquid; Raise the heating rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 42.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 180.0%.

Example 14

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of concentrated nitric acid + 1g of thiourea + 2g of pyrophosphoric acid in 50ml of water, and stir to dissolve in a water bath at 60°C to obtain an impregnating solution;

(2) Immerse 10g of coconut shell activated carbon into the impregnating solution, place it in a water bath at 60°C, seal and stir for 6h, filter and filter off the liquid; Raise the heating rate to 800°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 29.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 93.3%.

Example 15

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3 g of melamine + 10 g of 30% hydrogen peroxide + 2 g of thiourea + 2 g of triphenylphosphine in 50 ml of absolute ethanol, and stir to dissolve in a water bath at 60 ° C to obtain an impregnation solution;

(2) Immerse 10g of pitch-based spherical activated carbon into the impregnating solution, in a water bath at 60°C, impregnate with sealing and stirring for 6h, filter the liquid; The heating rate is raised to 800°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 45.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 200.0%.

Example 16

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 3g of pyrimidine in 20ml of water, and stir to dissolve in a water bath at 70°C to obtain an impregnation solution;

(2) Immerse 10g of pitch-based spherical activated carbon into the impregnating solution, in a 70°C water bath, seal and stir for 4h, filter and filter off the liquid; dry it, put it in a muffle furnace, and set it in a nitrogen atmosphere at 5°C/min The heating rate is raised to 700°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 38.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 153.3%.

Example 17

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 2g of purine in 20ml of water, and stir to dissolve in a water bath at 60°C to obtain an impregnation solution;

(2) Immerse 10g of coal-based activated carbon into the impregnating solution, in a water bath at 60°C, seal and stir for 4h, filter and filter off the liquid; Raise the heating rate to 600°C, keep it for 2 hours, and cool to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 26.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 73.3%.

Example 18

A preparation method for a non-metallic catalyst for acetylene hydrochlorination, comprising the steps of:

(1) Dissolve 2g of pyrrole in 20ml of acetone, and stir to dissolve in a water bath at 70°C to obtain an impregnation solution;

(2) Immerse 10g of pitch-based spherical activated carbon into the impregnating solution, in a 70°C water bath, seal and stir for 4h, filter and filter off the liquid; dry it, put it in a muffle furnace, and set it in a nitrogen atmosphere at 5°C/min The heating rate is raised to 700°C, kept for 2h, and cooled to room temperature to obtain a non-metallic catalyst for acetylene hydrochlorination;

The reaction conditions are hydrogen chloride activation for 30 minutes, acetylene space velocity of 180h ^-1 , reaction temperature of 170°C, raw material gas ratio V _C2H2 /V _HC1 =1:1.15. The loading amount of the above catalyst is 5ml; the catalyst catalyzes the hydrochlorination of acetylene under the above conditions, and the initial conversion rate of acetylene is 32.0%, and the selectivity of vinyl chloride is greater than 99.0%. Compared with the catalyst in Example 1 that does not support any non-metallic active components, the initial conversion rate of acetylene of the non-metallic catalyst of the present invention is increased by 113.3%.

Experiments have proved that the impregnation solution prepared by using N-methylpyrrolidone and benzene instead of acetone in this embodiment as solvent can also be used for the preparation of non-metallic catalysts for acetylene hydrochlorination.

Claims (8)

1., for a preparation method for the non-metallic catalyst of acetylene hydrochlorination, it is characterized in that comprising the steps:

(1) in proportion 0.1-10g is dissolved in 10-50ml solvent containing the nonmetallic compound of N, O, S and P at least one, is stirred to dissolve to obtain maceration extract; Described solvent is water, methyl alcohol, ethanol, formaldehyde, acetic acid, hot ethylene glycol, glycerine, pyridine, acetone, 1-METHYLPYRROLIDONE, ether, benzene, chloroform;

(2) immerse in described maceration extract by 10g catalyst carrier in proportion, at water-bath 30-100 DEG C, dipping 2-10h is stirred in sealing, filters liquid; Drying, puts into tube furnace or Muffle furnace, rises to 500-1000 DEG C in a nitrogen atmosphere with the heating rate of 4-6 DEG C/min, keeps 1-4h, is chilled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination.

2. the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination according to claim 1, is characterized in that the described nonmetallic compound containing N is melamine, urea, pyrroles, pyridine, pyrimidine or purine.

3. the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination according to claim 1, is characterized in that the described nonmetallic compound containing O is nitric acid or hydrogen peroxide.

4. the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination according to claim 1, is characterized in that the described nonmetallic compound containing S is thiocarbamide or mercaptan.

5. the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination according to claim 1, is characterized in that the described nonmetallic compound containing P is triphenylphosphine, sodium hypophosphite, pyrophosphoric acid or sodium pyrophosphate.

6. the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination according to claim 1, is characterized in that described catalyst carrier is cocoanut active charcoal, active carbon from coal, asphalt-base spherical activated carbon, CNT, carborundum, ZTCMS-185 type molecular sieve, ZTCMS-200 type molecular sieve or ZTCMS-220 type molecular sieve.

7. a kind of non-metallic catalyst for acetylene hydrochlorination of preparing of the described method of claim 1-6.

8. a kind of application of non-metallic catalyst in acetylene hydrochlorination reaction for acetylene hydrochlorination of claim 7.